Aromatic polyalkylene ethers



Patented Nov. 7, 1939 UNITED STATES PATENT OFFICE AROMATIC POLYALKYLENE ETHERS Herman A. Bruson, Philadelphia, Pa., assignor to Riihm Pa.

No Drawing.

& Haas Company, Philadelphia,

Application April 26, 1938,

Serial No. 204,307

16 Claims.

in which A is an aliphatic or cycloaliphatic hydrocarbon group, A is hydrogen, an aliphatic, cycloaliphatic, aromatic or arylaliphatic hydrocarbon group or an alkoxy group, R is an aromatic nucleus of the benzene, anthracene, phenanthrene,

--C1|H2n is a short chain alkylene radical having at least two carbon atoms and a: is an integer of from 1 to 5 inclusive. When such compounds are converted into wetting agents, etc. for example by sulfonation, it has been found that the most effective are those in which the sum of the aliphatic carbon atoms in A and A be at least four. Thus, if A is an aliphatic hydrocarbon group containing four or more carbon atoms, A may be hydrogen but is not necessarily so. If, on the other hand, A contains less than four carbon atoms, then A must be an aliphatic or cycloaliphatic hydrocarbon radical containing at leastenough aliphatic carbon atoms so that the total of such carbon atoms in A and A is at least four.

In the foregoing formula A may represent such groups as ethyl, propyl, butyl, amyl, hexyl, octyl, dodecyl, tctradecyl, hexadecyl, octadecyl, oleyl, or cycloaliphatic groups such as butyl-cyclohexyl, octyl-cyclohexyl, lauryl-cyclohexyl, cetyl-cyclohexyl, etc. or other alkyl group containing up to carbon atoms; bornyl, abietyl, decahylronaphthyl, tetrahydro-abietyl or other terpenic radical or a naphthenic radical. The alkyl groups mentioned above may have straight or branched chains and the O-CnH-in' group of the formula may be attached to a primary, secondary or tertiary carbon atom. A may also represent unsaturated groups corresponding to the saturated groups enumerated. A may represent hydrogen, an alkyl group such as ethyl, butyl, amyl and the other alkyl and cycloalkyl groups represented by A or it may represent an aromatic or arylaliphatic hydrocarbon group such as phenyl, benzyl, phenylethyl, phenylisobutyl and the like.

The alkylene group represented by -CnH2n-- contains at least two carbon atoms and may be a straight or branched chain radical such as are represented by the formulas:

n being an integer from 2 to 5.

naphthalene or other condensed ring series} invention may be prepared in either of the following ways:

(a) An aliphatic, cycloaliphatic or terpenic alcohol whose hydrocarbon radical corresponds to A in the formula may be condensed with an aromatic alkylene ether halide having the formula in which X is a halogen atom, in the presence of an alkali metal oxide or hydroxide so as to split out alkali metal halide, or the alkali alcoholate of thegalcohol A-OH may be condensed directly wth the aromatic alkylene ether halide, again splitting out the alkali metal halide.

(b) A phenolic compound corresponding to the formula may be condensed with an aliphatic or cycloaliphatic alkylene ether halide in the presence of an alkali so as to split out alkali metal halide.

When the process is carried out according to the description given in paragraph (a), that is by condensing an alcohol A-OH with an aromatic alkylene ether halide in the presence of an alkali, it is usually done by heating a mixture of about one mol each of the ingredients to a temperature of from 175 to 260 C. for a period of 5 to 20 hours depending on the reactivity of the particular materials used. The reaction mixture is then cooled, filtered to remove the alkali metal. halide and purified by distillation under reduced pressure.

When a phenol A'ROI-I is condensed with an aliphatic or cycloaliphatic alkylene ether halide A(O-CnH2n) :r-Cl

the ingredients along with the alkali are usually dissolved in a solvent such as ethanol or butanol and a small amount of water and heated to the boiling point of the solution.

Most of the products are pale or colorless oils of very high boiling point which on sulfonation of the aromatic nucleus, as disclosed in my copending application Serial No. 204,306 filed on even date herewith, yield powerful cleansing, emulsifying and dispersing agents which have a wide application in the textile, leather, dyeing and other industries.

The invention may be illustrated by the following examples but it is not limited to the exact materials or conditions of operation shown as it may otherwise be practiced within the scope of the appended claims. 4

, chlorodiethyl ether,

Example 1 It was a colorless oil, which on redistillation boiled at 210 to 220 C./2-3 mm. The yield was 117 g.

Example 2 A mixture consisting of 156 g. of 5-0:, a, v, 'ytetramethyl-butylphenoxy-ethoxyethyl chloride. 93 g, of lauryl alcohol,. and 22 g. of sodium hydroxide was heated for '7 hours at 190 to 200 C. as described in Example 1. The desired product, boiling at 250-265 C./3 mm., was collected as a colorless oil having the formula (3H3 (EH3 om-o-om-cOo-omom-o-cmom-o-oum.

Example 3 A mixture consisting of 100 g. of p-phenoxy-p'- 134 g. of oleyl alcohol and 30.8 g. of potassium hydroxide was heated with stirring under reflux for 15 hours at 190 to 220 C. After filtering off the precipitate, the filtrate was distilled in vacuo. The oil, boiling at 210- 240 C./0.1 mm., was collected as the desired product or the probable formula CuHnOCHsCH:-0CH1CH:O--GHr- (CHI)TCH=CH (CHI)T-OHS The analogous product made from cetyl alcohol, namely:

CeH5OCH2CH2O-CH2CH2OC16H33 has similar properties.

Example 4 A mixture consisting of 135.5 g. oi laurylphenol, 90.5 g. of p-butoxy-p'-chlorodiethyl ether, 20.5 g. of sodium hydroxide, 50 g. of ethyl alcohol, and 10 g. of water was boiled under reflux for 10 hours with vigorous agitation. When cool, the product was filtered and the filtrate was distilled under reduced pressure. The desired product, ,S-(laurylphenoxy-) -fi'-butoxy diethyl ether distilled over at 212-220 C./4 mm. as a colorless oil. Yield Example 5 A mixture consisting of 103 g. of p-cz,a,'y,'ytetramethyl-butylph'enol, 90.5 g. of p-butoxy-,3'- chlorodiethyl ether, 20.5 g. of sodium hydroxide, 50 g. of ethyl alcohol, and 10 cc. of water was boiled under reflux with stirring for 12 hours at C. The product, when cool, was filtered, and the filtrate distilled under reduced pressure. The fraction boiling at 205-210 C./4 mm. came over as a colorless oil having the formula Example 6 A mixture consisting of 85 g. of p-phenylphenol, 91 g. of p-butoxy-fi'-chlorodiethyl ether, 20.5 g. of caustic soda, 50 g. of ethyl alcohol, and 10 cc. of water was heated with agitation under reflux at 90 C. for 12 hours. The material was cooled, filtered, and the filtrate distilled. The product. boiling at 227-232 C./4 mm., is butoxy-ethoxyethoxy-diphenyl, having the formula can-o-omom-o-omcm-o-QO Example 7 A mixture consisting of 88 g. of p-cyclohexylphenol, 90.5 g. of e-butoxy-,3'-chlorodiethyl ether, 20.5 g. of caustic soda, 50 g. 01 butanol, and 10 cc. of water was boiled under reflux for 12 hours. The material was cooled, filtered, and the filtrate distilled. The product, boiling at 210-2l5 C./5 mm., weighed g. and is butoxyethoxyethoxyphenylcyclohexane, having the formula o.H.0-cmcm-o-omcm-o-Qmm.

Example 8 A mixture consisting of 90.5 g. of p-butoxy-p'- chlorodiethyl ether, 72. g. of p-naphthol, 20.5 g. of caustic soda, 50 g. of butanol, and 10 cc. oi! water was boiled for 12 hours under reflux. The cooled, filtered product was distilled in vacuo. 72 g. of p-butoxy-ethoxyethoxy naphthalene, boiling at 221-230 C./5 mm. was obtained, having the formula Example 9 A mixture consisting of 103 g. of p-ter.octylphenol (made by condensing diisobutylene and phenol), 54 g. of p-chlorodiethyl ether, 20.5 g. of caustic soda, 50 g. of butanol, and 10 cc. of water, was boiled under reflux for 10 hours. The cooled, filtered product yielded, upon distillation, 70 g. of the ether having the formula CH: C

I cam-o-cmcm-o-Qi-cm-e-cm H. CH: boiling at -157 C./2 mm. as a colorless oil.

Example 10 The compound v CsH5OCH2CH2OCH2CH2O-C10Hi'i (B. P. 185-l95 C./3 mm.) was made by condensing borneol in the presence of caustic soda with ,B-phenoxy-B'-chlorodiethyl ether.

Example 11 A mixture consisting of 178 g. of p-a,a,'y,'ytetramethyl butylphenoxy ethoxy-ethoxyethyl chloride 21 g. of sodium hydroxide and 81 g. of diethylene glycol monobutyl ether was heated with stirring for 10 hours at 180 to 210 C., under reflux. The

reaction product was washed, and fractionally distilled in vacuo. The product benzene nucleus and as is an integer of from 1 to 5 inclusive.

came over at 262-280" C./3 m. as a pale yellow oil, which upon redistillation boiled at 260-265 C./3 mm. Example 12 A mixture consisting of 68 g. of p-u,a,'y,' tetramethyl-phenoxyisopropyl-isopropyl chloride C3H1?-C0H4-O-CHzCH(CHs)O-CH(CHa)CHzCl 324 g. of diethylene glycol monobutyl ether, and

11.7 g. of potassium hydroxide was heated under reflux with stirring for 10 hours at 230 to 240 C. The reaction product was washed and distilled in vacuo. The product CHz-OCzH4-0CzHaO-C;Ha

distilled over at 235-240 C./ 2 mm. as a pale yellow oil.

I claim: 1. Compounds of the general formula in which A represents a member of the group 3 consisting of aliphatic and cycloaliphatic hydrocarbon radicals, A represents a member of the group consisting of hydrogen, aliphatic, cycloaliphatic, aryl and arylaliphatic hydrocarbon radicals, the sum of the aliphatic carbon atoms in A and A being at least four, R is an aromatic nucleus, CnH2nis an alkylene group containing from two to five carbon atoms inclusive, and a: is an integer from 1 to 5 inclusive.

2. Compounds of the general formula in which A represents a member of the group consisting of aliphatic and cycloaliphatic hydrocarbon radicals, A represents a member of the group consisting of hydrogen, aliphatic, cycloaliphatic, aryl, and arylaliphatic hydrocarbon radicals, the sum of the aliphatic carbon atoms in A and A being at least four, R is an aromatic nucleus, and :r is an integer from 1 to 5 inclusive.

3. Compounds of the general formula in which A represents a member of the group consisting of aliphatic and cycloaliphatic hydrocarbon radicals, A' represents a member of the group consisting of hydrogen, aliphatic, cycloaliphatic, aryl and arylaliphatic hydrocarbon radicals, the sum of the aliphatic carbon atoms in which A is an aliphatic hydrocarbon radical containing at least four carbon atoms, R is a 6. Lauryloxy-ethoxy-ethoxy-ethoxy benzene.

7. Oleyloxy-ethoxy-ethoxy benzene.

8. Cetyloxy-ethoxy-ethoxy benzene.

9. The process of preparing aromatic alkylene ethers having the general formula A-(o-c'nnzn 1-ORA' in which A represents a member of the group consisting of aliphatic and cycloaliphatic hydro carbon radicals, A represents a member of the group consisting of hydrogen, aliphatic, cycloaliphatic, aryl, and arylaliphatic hydrocarbon radicals, the sum of the aliphatic carbon atoms in A and A being at least four, R is an aromatic nucleus, --C1LH2n is an alkylene group containing from two to five carbon atoms inclusive, and :c is an integer from 1 to 5 inclusive, which comprises heating an alcohol of the formula A-OH with an aromatic alkylene ether halide of the formula in which X is a halogen atom in the presence of an alkali so as to split out alkali metal halide.

10. The process of preparing aromatic alkylene ethers having the general formula in which A represents a member of the group consisting of aliphatic and cycloaliphatic hydrocarbon radicals, A represents a member of the group consisting of hydrogen, aliphatic, cycloaliphatic, aryl, and arylaliphatic hydrocarbon radicals, the sum of the aliphatic carbon atoms in A and A being at least four, R is an aromatic nucleus, and a: is an integer from 1 to 5 inclusive, which comprises heating an alcohol of the formula A-OH with an aromatic alkylene ether halide of the formula in which X is a halogen atom in the presence of an alkali so as to split out alkali metal halide.

11. The process of preparing aromatic alkylene ethers having the general formula in which A represents a member of the group consisting of aliphatic and cycloaliphatic hydrocarbon radicals, A' represents a member of the group consisting of hydrogen, aliphatic, cycloaliphatic, aryl, and arylaliphatic hydrocarbon radicals, the sum of the aliphatic carbon atoms in A and A being at least four, and R. is an aromatic nucleus, which comprises heating an alcohol of the formula AOH with an aromatic ether chloride of the formula in the presence of an alkali so as to split out alkali chloride.

12. The process of preparing aromatic alkylene ethers having the general formula A- 0-oH2oH20- CHzCH2-()CH2CHzO R-A' in which A represents a member of the group consisting of aliphatic and cycloaliphatic hydro carbon radicals, A represents a member of the group consisting of hydrogen, aliphatic, cycloaliphatic, aryl, and arylaliphatic hydrocarbon radicals, the sum of the aliphatic carbon atoms in A and A being at least four, and R is an aromatic nucleus, which comprises heating an 5 alcohol of the formula AOH with an aromatic alkylene ether chloride of the formula A'R-ocH,0H,-0-cmom-o-cmomm in the presence of an alkali so as to split out alkali chloride.

13. The process of preparing aromatic alkylene ethers having the general formula A(OCH2CH2) 1-OR in which A is an aliphatic hydrocarbon radical containing at least four carbon atoms, R is a benzene nucleus and a: is an integer of from 1 to 5 inclusive, which comprises heating an alcohol of the formula AOH with an aromatic alkylene ether chloride of the formula alcohol with phenoxy-ethoxy-ethyl chloride in the presence of sodium hydroxide so as to split out sodium chloride.

HERMAN A. BRUSON. 

